Polyureas and water-soluble or water-dispersible polymeric salts

ABSTRACT

The present invention relates to polymers, polyureas and water-soluble or water-dispersible polymeric salts, a cosmetic or pharmaceutical composition which comprises at least one such polymer, and to the use of the polymers.

[0001] The present invention relates to polyureas and water-soluble orwater-dispersible polymeric salts, to the use of these polymers, and tocompositions which comprise these polymers.

[0002] In cosmetics, polymers with film-forming properties are used forsetting, shaping and improving the structure of hair. Thesehair-treatment compositions generally comprise a solution of the filmformer in an alcohol or a mixture of alcohol and water.

[0003] Hair-treatment compositions, in particular hair-settingcompositions, are generally sprayed onto the hair in the form ofaqueous-alcoholic solutions. After the solvent has evaporated, the hairis held in the desired shape at the mutual points of contact by thepolymer which remains. The polymers should on the one hand besufficiently hydrophilic that they can be washed out of the hair, but onthe other hand they should be hydrophobic so that the hair treated withthe polymers retains its shape even at high atmospheric humidity, anddoes not stick together. In order to obtain as highly an efficienthair-setting action as possible, it is also desirable to use polymerswhich have a relatively high molecular weight and a relatively highglass transition temperature (at least 10° C.).

[0004] A further current demand on hair-treatment compositions is thatthey should give the hair flexibility, a natural appearance and shine,even, for example, when the hair is by its very nature particularlystrong and/or dark.

[0005] A further consideration when formulating hair-settingcompositions is that, because of the environmental regulations governingthe emission of volatile organic compounds (VOC) into the atmosphere, itis necessary to reduce the content of alcohol and propellant.

[0006] It is known to use water-soluble or dispersible polyurethanes incosmetics. Thus, because, for example, they have film-forming propertiesand, in general, a low viscosity in water/ethanol, they are suitable foruse in hair cosmetics, such as, for example, for formulating low-solventhair sprays.

[0007] DE-A-42 25 045 and WO 94/03515 describe the use of water-solubleor water-dispersible anionic polyurethanes as hair-setting agents.

[0008] The acid groups present in these polyurethanes can be convertedinto the corresponding salts by neutralization with at least one base.For this purpose, low molecular weight amines, such as2-amino-2-methylpropanol, diethylaminopropylamine andtriisopropanolamine, are used.

[0009] EP-A-619 111 describes the use of polyurethanes based on organicdiisocyanates, diols and 2,2-hydroxymethyl-substituted carboxylates inhair fixative compositions. Here, at least some of the carboxyl groupsare neutralized with an organic or inorganic low molecular weight base.

[0010] DE-A-195 41 658 describes water-soluble or water-dispersiblegraft polymers of a polyurethane prepolymer having terminal isocyanategroups and a protein containing free amino groups.

[0011] EP-A-636 361 describes a cosmetic composition comprising, in acosmetically compatible carrier, at least one pseudolatex based on apolycondensate which comprises at least one polysiloxane unit and atleast one polyurethane and/or polyurea unit having anionic or cationicgroups. The neutralizing agents used here are mineral bases, lowmolecular weight amines and aminoalcohols, mineral acids and lowmolecular weight carboxylic acids. WO 97/25021 has a similar disclosurecontent. The wash-off of these film formers is unsatisfactory. Inaddition, because they have a high siloxane content they do not have thesetting action required of a hair polymer.

[0012] DE-A-195 41 329 and WO 97/17052 describe hair-treatmentcompositions comprising a hair-setting polymer which is soluble ordispersible in water or in a water/alcohol mixture, and additionally awater-soluble or -dispersible siloxane-containing salt. Hairsprayformulations based on these siloxane-containing salts, anon-siloxane-containing hair-setting polymer and a silicone oil lead tovery smooth films.

[0013] DE-A-195 41 326 and WO 97/17386 describe water-soluble orwater-dispersible polyurethanes having terminal acid groups, theirpreparation and their use. Here, a water-soluble or -dispersiblepolyurethane prepolymer having terminal isocyanate groups is reactedwith an aminosulfonic acid or aminocarboxylic acid, in particulartaurine, aspartic acid and glutamic acid.

[0014] DE-A-197 09 277 relates to polysiloxane-containing hair-settingcompositions comprising from 0.5 to 15% by weight of carboxyl-containingpolymers which, in neutralized form, are water-soluble orwater-dispersible. The neutralizing agents used here are alkali metalcarbonates, ammonia and amines and amino alcohols having at most 3carbon atoms in the longest carbon chain.

[0015] None of the abovementioned documents describes polymeric salts ofa polymeric cation and a polymeric anion, where polyurea or polyurethaneis the polymeric anion and/or the polymeric cation. The polyurethanesdescribed above lead to films which are in need of improvement withregard to their flexibility and thus with regard to the supplenessimparted to the hair.

[0016] It is known to use copolymers based on α,β-ethylenicallyunsaturated mono- and/or dicarboxylic acids in haircare compositions,

[0017] GB-A-1 321 836 describes hair-setting compositions based oncopolymers which comprise an unsaturated dicarboxylic acid and a vinylor vinylidene monomer in copolymerized form. From 5 to 20% of thecarboxyl groups have been neutralized with primary C₄- to C₁₆-amines.

[0018] DE-A-29 17 504 describes an aerosol hairspray based on acopolymer of at least one unsaturated monocarboxylic acid and at leastone vinyl or vinylidene monomer. Here, at least 7 to 100% of thecarboxyl groups have been neutralized, at least half of which with along-chain primary, secondary and/or tertiary amine having from 8 to 20carbon atoms in the longest chain.

[0019] WO 89/12438 describes a hair-setting composition based on a hairpolymer containing carboxyl groups which have been neutralized to atleast 40 mol % with a long-chain amine chosen from amidoamines,N-ethoxylated amines and ether amines.

[0020] The abovementioned polyacrylates having carboxyl groups whichhave been neutralized with fatty amines or ethoxylated fatty amines leadto soft, tacky films with a drastically reduced setting action. Thesepolymers are therefore of only very limited suitability for use ashair-setting agents.

[0021] JP-A-7127480 describes a hair-treatment composition based on anamine salt solution of a copolymer which comprises an unsaturatedcarboxylic acid in copolymerized form.

[0022] JP-A-03206023 describes a polymer resin for hair-treatmentcompositions which comprises, in copolymerized form, a) 6 to 35% byweight of acrylic acid, methacrylic acid, itaconic acid or a mixturethereof, b) 15 to 50% by weight of at least one C₁₀- to C₁₈-alkyl(meth)acrylate, c) 15 to 50% by weight of at least one C₄- to C₈-alkyl(meth)acrylate and d) 0 to 25% by weight of at least one otherhydrophobic vinyl monomer. The resulting copolymers are neutralized witha base chosen from ammonia, morpholine, isopropanolamine andaminoethylpropanediol.

[0023] JP-A-03206024 describes a hair-setting polymer similar to that inJP-A-03206023, which additionally comprises from 5 to 50% by weight ofan N-alkyl-substituted acrylanide. The hair-setting polymers describedin both of these documents have a high content of hydrophobic monomers.Their wash-off is therefore in need of improvement.

[0024] DE-A-39 01 325 and DE-A-42 14 305 describe hair-settingcompositions which comprise, as film former, a copolymer based ontert-butyl (methy)acrylate and (meth)acrylic acid, where the carboxylgroups of the copolymers have been partially or completely neutralizedby amines. Here, the amines are chosen from mono-, di- ortrialkanolamines, alkanediolamines or primary, secondary or tertiaryalkylamines. Films based on these polyacrylates are generally hard anddo not exhibit flexibility and, particularly with regard to theirsetting action, are in need of improvement.

[0025] DE-A-197 09 277 describes polysiloxane-containing hair settingcompositions based on carboxyl-containing polymers, polysiloxanes havingprimary, secondary or tertiary amino groups, and low molecular weightneutralizing agents. The use of siloxanediamines which have not beenfurther functionalized in hair setting compositions leads to crosslinkedproducts which are difficult to wash out. Because of poor adhesion, thesetting action of these formulations is in need of improvement.

[0026] U.S. Pat. No. 4,761,273 relates to mixtures of an anionic and acationic polymer, where the anionic polymer is a polyacrylate or aderivative thereof, and the cationic polymer is a polyamine or aderivative thereof. These polymer salts are soft and more tacky thanthose according to the invention.

[0027] It is an object of the present invention to provide polymers.These should be suitable as a cosmetic composition, or for use incosmetic compositions, in particular hair-treatment composition(s).Preferably, they should form films with good flexible properties andshould be tack-free so that hair-treatment compositions based thereonimpart elasticity to the hair. The polymers according to the inventionshould impart specific properties to the hair: natural hold, goodcombability, good feel and suppleness. This is the case particularly forpolymers for hairspray formulations. For certain types of hair in theUSA and Asia, polymers with increased flexibility are desired.

[0028] Surprisingly we have found that this object is achieved bycertain polyureas and water-soluble or water-dispersible polymericsalts.

[0029] The present invention therefore relates to a polyurea constructedfrom:

[0030] a) a diamine which contains a group—(—CH₂CH₂O—)_(n)-(C₃H₆-O—)_(m), where the order of the alkylene oxideunits is arbitrary and m and n independently of one another are aninteger between 0 and 50, and m+n is between 5 and 60, and

[0031] b) at least one amino-containing or hydroxyl-containingpolysiloxane and

[0032] c) at least one diisocyanate, and

[0033] d) optionally a di-, tri- or tetramine or polyamine whichcontains at least one ionogenic group, and

[0034] e) optionally one or more diamines having a molecular weight offrom 60 to 6000 g/mol,

[0035] where the polyurea contains at least one ionogenic or ionicgroup.

[0036] Preference is given to polyureas which contain at least one freeamine group.

[0037] In addition, the invention relates to a process for thepreparation of the abovementioned polyureas, where the polymerization iscarried out in alcohol or water/alcohol solution at a temperature ofless than or equal to 50° C. and, in the case of hydroxyl-containingpolysiloxane, components b) and c) are firstly reacted with one another.

[0038] The invention further relates to the use of neutralized polyureaas film-forming auxiliary as additive for cosmetic preparations. Inaddition, the invention relates to the use of polyurea having ionic orionogenic groups as neutralizing agent for polymers which contain ionicor ionogenic groups.

[0039] The invention relates to water-soluble or water-dispersible saltscomprising

[0040] A) a base polymer which contains an ionic or ionogenic group, and

[0041] B) a neutralizing polymer which partially neutralizes the ionicor ionogenic group of the base polymer A, where the ionogenic or ionicgroups of A are more frequent by a factor of from 2 to 30 than theionogenic groups of the neutralizing polymer B.

[0042] Both the base polymer and the neutralizing polymer can be(partially) neutralized by adding neutralizing agents. As a rule, inthis connection, the base polymer is firstly (partially) neutralized byadding a neutralizing agent, and then the neutralizing polymer is added.It is also possible to add the neutralizing polymer to the base polymerand then to neutralize with neutralizing agents. Particular preferenceis given to the (partial) neutralization of the base polymer and thesubsequent addition of the neutralizing polymer. The neutralizing agentused is preferably a mixture of different neutralizing agents.

[0043] In a preferred embodiment, the base polymer A and/or theneutralizing polymer B is a polyurea or a polyurethane. In aparticularly preferred embodiment, the base polymer A and/or theneutralizing polymer B is a polyurea as claimed in claim 1.

[0044] Neutralizing agents which can be used are:

[0045] If anionogenic or ionic groups are present in excess,neutralization is carried out with an amine or amine mixture (e.g.amino-2-methylpropanol AMP, ethylenediamine etc.) and/or with a base(NaOH, KOH etc.).

[0046] Preferably, polymers with anionogenic groups are neutralizedusing mixtures which contain at least an amine, preferably ahydroxyl-containing amine, such as amino-2-methylpropanol, mono-, di-and triethanolamine, or a diamine, such as ethylenediamine, and analkali metal hydroxide, preferably potassium hydroxide. Polyurethaneswith anionogenic groups are preferably further neutralized usingmixtures which contain at least one amine and an amino alcohol,preferably 2-amino-2-methyl-1-propanol.

[0047] If cationogenic or cationic groups are present in excess,neutralization is carried out with an acid or acid mixture (e.g. lacticacid, phosphoric acid etc.).

[0048] The amines, acids and/or bases are preferably cosmeticallycompatible.

[0049] An amine value of less than the acid number is particularlypreferred.

[0050] Cosmetically compatible acids and polyacids are known to theperson skilled in the art and are listed, for example, in WO 97/17052and are incorporated herein. Cosmetically compatible amines are likewiseknown to the person skilled in the art and are also listed in thepresent application.

[0051] The base polymer A can be a polyurethane, polyurea orpoly(urethane/urea) constructed from:

[0052] f) at least one compound which contains two (or more) activehydrogen atoms per molecule,

[0053] g) at least one compound which contains two active hydrogen atomsper molecule and has a molecular weight of from 56 to 300 g/mol,

[0054] h) at least one phosphate-, phosphonate-, carboxylate-, sulfate-,and/or tert-amine-containing compound or compounds thereof which containthe free acids that contain two active hydrogen atoms per molecule, and

[0055] i) at least one diisocyanate.

[0056] Or the base polymer A is a polyacrylate constructed from:

[0057] at least one C₁-C₄-alkylacrylic ester or C₁-C₄-alkylmethacrylicester or acrylamide or methacrylamide or C₁-C₄-alkylacrylamide orC₁-C₄-alkylmethacrylamide,

[0058] at least one COOH-containing monomer.

[0059] Preference is given to polyacrylates comprising 65-90% by weightof ester or amide and 10-35% by weight of COOH-containing monomer.

[0060] The preferred esters are C₄-alkylacrylic esters orC₄-alkylmethacrylic ester.

[0061] The preferred amides are C₄-alkylacrylamides orC₄-alkylmethacrylamides.

[0062] The neutralizing polymer used is preferably a film-formingpolymer which is dispersible with water.

[0063] The invention further relates to polyurethane, poly(urethaneurea)or polyurea as neutralizing polymer B, constructed from:

[0064] j) at least one compound or a mixture of compounds having atleast two active hydrogen atoms per molecule and having a molecularweight of from 56 to 6000 g/mol, where at least one compound containsone of the following groups:

[0065] —(—CH₂-CH₂O—)m-(C₃H₆O—)n—, where the order of the alkylene oxideunits is arbitrary, and m and n independently of one another are aninteger from 0 to 50, and the sum m+n is in the range from 5 to 60,

[0066] —COO⁻, —SO₃ ⁻ or

[0067] —N⁺ group (quaternized amines),

[0068] k) if necessary a compound having at least two active hydrogenatoms per molecule and at least one ionogenic group,

[0069] l) at least one amino-containing poly(dimethylsiloxane) and

[0070] m) at least one diisocyanate,

[0071] where the (acid value or amine value is not greater than 60.

[0072] In this neutralizing polymer, the components are preferablypresent in the following amounts:

[0073] j) 10 to 90% by weight, preferably 15 to 80% by weight,

[0074] k) 0 to 20% by weight, preferably 0 to 10% by weight,

[0075] l) 0.1 to 30% by weight, preferably 0.3 to 20% by weight,

[0076] m) 5 to 30% by weight,

[0077] based on j+k+l+m.

[0078] In a preferred embodiment of the invention, the neutralizingpolymer is constructed from at least one vinyllactam and/or at least onevinylamide and at least one amine-containing monomer, the amine valuebeing between 1 and 60.

[0079] In particular, such a neutralizing polymer can be constructedfrom:

[0080] a) 25 to 80% by weight of at least one vinyllactam and/orvinylamide, preferably vinylpyrrolidone and/or vinylcaprolactam,

[0081] b) 1 to 20% by weight of at least one amine-containing monomer,

[0082] c) 0 to 40% by weight of a C₁-C₄-alkylacrylic ester orC₁-C₄-alkylmethacrylic ester or acrylamide or methacrylamide orC₁-C₄-alkylacrylamide or C₁-C₄-alkylmethacrylamide, preferably acorresponding C₄-alkyl ester and C₄-alkylamide,

[0083] where the amine value is between 1 and 60.

[0084] In a further preferred embodiment, the neutralizing polymer isconstructed from at least one C₁-C₁₈-allylmethacrylic ester and/orC₁-C₁₈-alkylmethacrylamide and at least one amine-containing and/orCOOH-containing monomer.

[0085] The invention also relates to processes for the preparation ofthe abovementioned polymeric salts, where the base polymer is partiallyneutralized in a suitable solvent (water or alcohol/water) with amonovalent neutralizing agent, and then the neutralizing polymer isadded.

[0086] Preference is given to a process for the preparation of apolymeric salt in which a vinyllactam-carrying polymer is used asneutralizing polymer, where an anionic or ionogenic base polymer(preferably one carrying carboxylate groups) is preferably neutralizedat a temperature of about 80° C. for about 1 h in water oralcohol/water, and is then neutralized with a low molecular weightamine. The organic solvents can be removed after the addition of water,for example by distillation under reduced pressure. The aqueous solutionor dispersion of the polymeric salt can be used to obtain the polymericsalt (e.g. by spray drying).

[0087] The polymeric salts according to the invention are at leastpartially crosslinked. The crosslinking here is via ionic bondingbetween anionic groups of at least two different polymer chains of apolymer (base or neutralizing polymer) and at least two cationic groupsof the other polymer (neutralizing or base polymer).

[0088] The amines always have at least two primary, secondary and/ortertiary amino groups which are able to form cationic groups.

[0089] Component f) of the base polymer based on polyurethanes ispreferably a polymer having a number-average molecular weight in therange from about 300 to 5000, preferably from about 400 to 4000, inparticular from 500 to 3000 g/mol. Polymers f) which can be used are,for example, polyester diols, polyetherols, polyamidediamines,polysiloxane polyol/polyamines and mixtures thereof. Polyetherols arepreferably polyalkylene glycols, e.g. polyethylene glycols,polypropylene glycols, polytetrahydrofurans etc., copolymers of ethyleneoxide and propylene oxide or block copolymers of ethylene oxide,propylene oxide and butylene oxide which contain the copolymerizedalkylene oxide units in random distribution or in the form of blocks.Also suitable are α,ω-diamino polyethers, which can be prepared byamination of polyalkylene oxides with ammonia. Preference is given tousing polyester-diols and mixtures which contain these as component f).

[0090] Suitable polytetrahydrofurans can be prepared by cationicpolymerization of tetrahydrofuran in the presence of acidic catalystssuch as, for example, sulfuric acid or fluorosulfuric acid. Suchpreparation processes are known to the person skilled in the art.

[0091] Preferred polyester-diols have a number-average molecular weightin the range from about 400 to 5000, preferably 500 to 3000, inparticular 600 to 2000.

[0092] Suitable polyester-diols are all those which are customarily usedfor the preparation of polyurethanes, in particular those based onaromatic dicarboxylic acids, such as terephthalic acid, isophthalicacid, phthalic acid, Na or K sulfoisophthalic acid etc., on aliphaticdicarboxylic acids, such as adipic acid or succinic acid etc., and oncycloalphatic dicarboxylic acids, such as 1,2-, 1,3- or1,4-cyclohexanedicarboxylic acid. Suitable diols are particularlyaliphatic diols, such as ethylene glycol, propylene glycol,1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethyleneglycols, polypropylene glycols, 1,4-dimethylolcyclohexane.

[0093] Preference is given to polyester-diols based on aromatic andaliphatic dicarboxylic acids and aliphatic diols, in particular those inwhich the aromatic dicarboxylic acid makes up from 10 to 95 mol %, inparticular from 40 to 90 mol %, of the total dicarboxylic acid content(remainder is aliphatic dicarboxylic acids).

[0094] Particularly preferred polyester-diols are the reaction productsof phthalic acid and diethylene glycol, isophthalic acid/adipic acid and1,6-hexanediol and/or neopentyl glycol, isophthalic acid/adipic acid and1,4-dimethylolcyclohexane and/or neopentyl glycol, isophthalicacid/adipic acid and 1,4-dimethylolcycohexane and/ordimethylolcyclohexane and/or diethylene glycol, adipic acid and1,6-hexanediol and/or neopentyl glycol and/or 1,4-dimethylolcyclohexaneand/or diethylene glycol, polyamidediamine, in particular diamine ofitaconic acid/aliphatic diamines, e.g. itaconic acid/hexanediamine(1,6).

[0095] The polysiloxanes are preferably a compound of the formula I

[0096] in which

[0097] R¹ and R² independently of one another are C₁-C₄-alkyl, benzyl orphenyl,

[0098] E¹ and E² independently of one another are OH or NHR³, where R³is hydrogen, C₁- to C₆-alkyl or C₅- to C₈-cycloalkyl,

[0099] a and b independently of one another are from 2 to 8,

[0100] c is from 3 to 50,

[0101] and mixtures thereof.

[0102] In the amino-containing polysiloxanes, at least E¹ or E² is NHR³.

[0103] In the hydroxyl-containing polysiloxanes, at least E¹ or E² is—OH.

[0104] Suitable alkyl radicals are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl etc. Suitablecycloalkyl radicals are, for example, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl etc.

[0105] Preferably, R¹ and R² are both methyl.

[0106] These polysiloxanes preferably have a nwnber-average molecularweight in the range from about 300 to 5000, preferably 400 to 3000.

[0107] The polysiloxanes are furthermore preferably a compound of theformula II

[0108] in which

[0109] the order of the siloxane units is arbitrary,

[0110] d is a value from 5 to 200, preferably 10 to 100,

[0111] e is a value from 1 to 20, preferably from 2 to 10,

[0112] Z is a radical of the formula —(CH₂)_(f)-NH₂ in which f is anumber from 1 to 10, preferably from 2 to 6, or

[0113] Z is a radical of the formula —(CH₂)_(g)-NH-(CH₂)_(h)-NH₂ inwhich g and h independently of one another are from 0 to 6, preferably 2to 3, or

[0114] Z is (CH₂)_(f)-(CH₂-CH₂O)_(n)-(C₃H₆O)_(m)-H, in which n+m is inthe range between 5 and 60, and m and n independently of one another arebetween 0 and 50.

[0115] These include, for example, the MAN and MAR brands fromDegussa-Hüls and the Finish brands from wacker, e.g. Finish WT 1270 andBelsil 6031 from Wacker.

[0116] Suitable polysiloxanes are also the polydimethylsiloxanesdescribed in EP-A-227 816, to which reference is hereby made.

[0117] Suitable diamines are, for example, ethylenediamine,propylenediamine 1,4-diaminobutane, 1,5-diaminopentane and1,6-diaminohexane.

[0118] Suitable polyamines are compounds of the following formula:

[0119] in which

[0120] p is an integer from 0 to 4,

[0121] R³ and R⁴ independently of one another are hydrogen, C₁- toC₄₀-alkyl or C₆- to C₄₀-alkenyl, where the alkyl and alkenyl radicalscan carry at least one ionogenic and/or ionic group which is chosen from—COOY, —SO₃Y and —PO₃Y, where Y is H, Li, Na, K or ammonium, where, whenp=0, at least one of the radicals R³ or R⁴ is a C₁- to C₄₀-alkyl or C₆-to C₄₀-alkenyl radical which carries at least one ionogenic and/or ionicgroup,

[0122] R⁵ and R⁷ are a C₂- to C₆-alkylene radical, where, when p is >1,the radicals R⁷ are independently chosen from C₂- to C₆-alkyleneradicals,

[0123] R⁶ is C₁- to C₆-alkyl, C₅- to C₈-cycloalkyl, phenyl orphenyl-C₁-C₄-alkyl, where, when p is >1, the radicals R⁶ areindependently chosen from these meanings.

[0124] If the polyamine of the above formula has two or more repeatunits N(R⁶)-R⁷_(p), then these can have identical or differentmeanings.

[0125] Preferably, p is 1, 2 or 3, in particular 1 or 2.

[0126] When p is 0, then the radicals R³ and R⁴ are independentlypreferably a C₁- to C₄₀-alkyl or C₆- to C₄₀-alkenyl radical, each ofwhich carries at least one ionogenic and/or ionic group.

[0127] Preferably, R³ and R⁴ independently of one another are hydrogen,C₁- to C₃₀-alkyl, preferably C₁- to C₁₂-alkyl, in particular C₁- toC₈-alkyl or a radical of the formula

[0128] where Y is H, Li, Na, K or ammonium.

[0129] In particular, R³ and R⁴ independently of one another arehydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, n-pentyl, h-hexyl. Specifically, R³ and R⁴ are bothhydrogen.

[0130] Preferably, R⁵ is a C₂- to C₄-alkylene radical.

[0131] Preferably, R⁶ is methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, cyclohexyl, phenyl or benzyl.

[0132] Preferably, R⁷ is a C₂- to C₄-alkylene radical.

[0133] The polyamine used is preferably diethylenetriamine,N-methyldiethylenetriamine, N-ethyldiethylenetriamine,N,N,N′,N′-tetramethyldiethylenetriamine,N,N,N′,N′-tetraethyldiethylenetriamine, dipropylenetriamine,N-methyldipropylenetriamine, N-ethyldipropylenetriamine,N,N′-bis(3-aminopropyl)butane-1,4-diamine, triethylenetetramine,tetraethylenepentamine and mixtures thereof. The polyamine isparticularly preferably N-methyldipropylenetriamine.

[0134] Component g) of the base polymer having two active hydrogen atomsis preferably a diol, diamine, amino alcohol, or a mixture thereof. Themolecular weight of these compounds is in a range from about 56 to 300.If desired, up to 3 mol % of said compounds can be replaced by triols ortriamines.

[0135] Preference is given here to using diols. Diols which can be usedare, for example, ethylene glycol, propylene glycol, butylene glycol,neopentyl glycol, cyclohexanedimethylol, di-, tri-, tetra-, penta- orhexaethylene glycol and mixtures thereof. Preference is given to usingneopentyl glycol and/or cyclohexanedimethylol.

[0136] Suitable amino alcohols are, for example, 2-aminoethanol,2-(N-methylamino)ethanol, 3-aminopropanol, 4-aminobutanol,1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol,4-methyl-4-aminopentan-2-ol etc.

[0137] Suitable diamines are, for example, ethylenediamine,propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane and1,6-diaminohexane, and fatty diamines of the structure R-NH-(CH₂)₂₋₃-NH₂where R=C₈-C₂₂-alkyl or C₈-C₂₂-alkenyl radical.

[0138] Suitable compounds h) of the base polymer have two activehydrogen atoms and at least one anionogenic and/or anionic group permolecule or at least one cationogenic and/or cationic group permolecule.

[0139] Preferred compounds having two active hydrogen atoms and at leastone anionogenic and/or anionic group per molecule are, for example,compounds containing carboxylate and/or sulfonate groups. Particularlypreferred components containing two active hydrogen atoms are2,2-hydroxymethyl-substituted carboxylates, in particulardimethylolpropanoic acid and mixtures which contain dimethylolpropanoicacid.

[0140] Components containing two active hydrogen atoms which also can beused are compounds of the formula

H₂N(CH₂)_(w)-NH-(CH₂)_(x)-COO-M⁺

H₂N(CH₂)_(w)-NH-(CH₂)_(x)-SO₃-M⁺

[0141] in which w and x independently of one another are an integer from1 to 8, in particular 1 to 6, and M is Li, Na or K, and compounds of theformula

H₂N(CH₂CH₂O)_(y)(CH₂CH(CH₃)O)₂(CH₂)_(w)-NH-(CH₂)_(x)-SO₃-M⁺

[0142] in which w and x are as defined above, y and z independently ofone another are an integer from 0 to 50, where at least one of the twovariables y or z is >0. The order of the alkylene oxide units here isarbitrary. The last-named compounds preferably have a number-averagemolecular weight in the range from about 400 to 3000. A suitablecompound of this type is, for example, Poly ESP 520 from Raschig.

[0143] If desired, the polyurethanes can, in addition to or instead ofthe compounds containing ionogenic and/or anionic groups, also contain,in incorporated form, compounds which have at least two active hydrogenatoms and at least one cationogenic and/or cationic group, preferably atleast one nitrogen-containing group, per molecule. Thenitrogen-containing group is preferably a tertiary amino group or aquaternary ammonium group. Preference is given, for example, tocompounds of the formulae

[0144] in which

[0145] R⁸ and R⁹, which can be identical or different, areC₂-C₈-alkylene,

[0146] R₁₀, R¹³ and R¹⁴, which can be identical or different, areC₁-C₆-alkyl, phenyl or phenyl-C₁-C₄-alkyl,

[0147] R¹¹ and R¹², which can be identical or different, are H orC₁-C₆-alkyl,

[0148] o is 1, 2 or 3,

[0149] X⁻ is chloride, bromide, iodide, C₁-C₆-alkylsulfate or SO₄ ²⁻/2.

[0150] Particular preference is given to N-(C₁-C₆-alkyl)diethanolamines,such as methyldiethanolamine or N-alkyldialkylenetriamine, such asN-methyldipropylenetriamine.

[0151] The diisocyanate component (component c), i) and m)) is acustomary aliphatic, cycloaliphatic and/or aromatic diisocyanate, suchas tetramethylene diisocyanate, hexamethylene diisocyanate,methylenediphenyl diisocyanate, tolylene 2,4- and 2,6-diisocyanate andtheir isomeric mixtures, o-, m- and p-xylylene diisocyanate,1,5-naphthylene diisocyanate, 1,4-cyclohexylene diisocyanate,dicyclohexylmethane diisocyanate and mixtures thereof, in particularisophorone diisocyanate, hexamethylene diisocyanate and/ordicyclohexylmethane diisocyanate. If desired, up to 3 mol % of saidcompounds can be replaced by triisocyanates.

[0152] As is customary for the preparation of polyurethanes andpolyureas, it is possible to use chain extenders. Suitable chainextenders are, for example, hexamethylenediamine, piperazine,1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane,neopentanediamine and 4,4′-diaminodicyclohexylmethane.

[0153] The polyurethanes and polyureas described are preferablyobtainable by reacting the reactants for the diisocyanates with thediisocyanates under an inert-gas atmosphere in an inert solvent, e.g.methyl ethyl ketone in the case of compounds containing OH groups, andwater or an alcohol such as ethanol in the case of compounds containingNH groups, at temperatures of from 30° C. to 110° C., preferably at 40°C. to 100° C. in the case of compounds containing OH group and below 50°C., preferably at 5° C. to 30° C. in the case of compounds containing NHgroups. This reaction can optionally be carried out in the presence ofchain extenders in order to prepare polyurethanes or polyureas withhigher molecular weights. The reaction can be accelerated by addingcatalysts such as organotin compounds, e.g. dibutyltin dilaurate,tetraalkyl titanates in particular in the case of reactants containingOH groups. As is customary in the preparation of polyurethanes, thereactants for the diisocyanates and the diisocyanates themselves areexpediently used in the molar ratio from 0.8 to 1.1:1.

[0154] The reaction can, in the case of polyurethanes, be carried outwithout solvent or in a suitable inert solvent or solvent mixture.Suitable solvents are aprotic polar solvents, e.g. tetrahydrofuran,ethyl acetate, N-methylpyrrolidone, dimethylformamide and, preferably,ketones, such as acetone and methyl ethyl ketone. The reaction ispreferably carried out under an inert-gas atmosphere, such as, forexample, under nitrogen. In addition, the reaction preferably takesplace at ambient pressure or under increased pressure. The componentsare preferably used in amounts such that the ratio of NCO equivalent ofthe compounds of the diisocyanate to equivalent of active hydrogen atomof the other components is in a range from about 0.6:1 to 1.4:1,preferably from 0.8:1 to 1.2:1, in particular from 0.9:1 to 1.1:1. Ifnecessary, any free isocyanate groups which are still present in thepolyurethanes can be deactivated by subsequent reaction with amines,preferably aminoalcohols. Suitable amines and aminoalcohols are thosementioned above, preferably 2-amino-2-methyl-1-propanol ortert-amine-containing diamine, such as N,N-dimethylaminopropyldiamine.

[0155] The polyurethanes and polyureas described are, because of theirionogenic groups, in particular when charges are present, usuallyreadily alcohol- and water-soluble or at least dispersible in alcoholand water without the assistance of emulsifiers. The alcohols intendedhere are, in particular, short-chain C₁-C₄-alkanole such as methanol,ethanol, isopropanol or n-propanol. Charged cationic groups can beproduced in the polyureas from the tertiary amine nitrogen atoms presenteither by protonation, e.g. using phosphoric acid or carboxylic acidsuch as lactic acid, or by quaternization, e.g using alkylating agentssuch as C₁- to C₄-alkyl halides or C₁- to C₄-alkyl sulfates. Examples ofsuch alkylating agents are ethyl chloride, ethyl bromide, methylchloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Theanionic or anionogenic groups are present in the corresponding amine.Since some of the polyurethanes and polyureas described are novelsubstances, the present invention further relates to these novelsubstances.

[0156] By neutralization of anionogenic groups of different basepolymers A) by an amino group of each amine (neutralizing agent), atleast some of the polymer chains are crosslinked, with salt formation.

[0157] Suitable neutralizing agents for the (partial) neutralization ofthe anionogenic base polymers are all the amines listed under theneutralizing agents; these can be used in each case individually or inthe form of mixtures. To neutralize the anionogenic groups of the basepolymers, it is also possible to use mixtures which contain at least oneamine and at least one other base. Suitable other bases for theneutralization of the polymers are alkali metal bases, such as sodiumhydroxide solution, potassium hydroxide solution, sodium carbonate,potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate and alkaline earth metal bases, such as calciumhydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate,and ammonia and amines which do not form a counterion B.

[0158] If the base polymer used is a polyurethane, poly(urethane-urea)or polyurea which additionally has amino groups as cationogenic groups,then these can be partially or completely converted into thecorresponding cationic groups by neutralization with an acid such aslactic acid or phosphoric acid, or by quaternization.

[0159] Polyurethanes, poly(urethane-urea) or polyurea which have bothcationogenic and anionogenic groups can be successively subjected toneutralization with at least one acid, neutralization with at least onebase and if desired additionally quaternization. The order of theneutralization steps is generally arbitrary in this case.

[0160] If desired, cationogenic groups can also be partially orcompletely quaternized. The quaternization can, for example, be carriedout using alkylating agents, such as C₁- to C₄-alkyl halides orsulfates. Preferred alkylating agents are ethyl chloride, ethyl bromide,methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.

[0161] The proportion of the polymeric salt in the neutralizing polymeris preferably at least about 1% by weight, in particular at least 3% byweight.

[0162] Preferably, the proportion of the polymeric salt in theneutralizing polymer is at most about 50% by weight, preferably at mostabout 40% by weight.

[0163] The water-soluble or water-dispersible polymeric salts accordingto the invention are obtainable by reaction of the base polymers,containing ionogenic and/or anionic groups bonded to the polymer chain,with at least one neutralizing polymer. The reaction can preferably becarried out immediately after the preparation of the base polymers andis generally carried out in the same reaction vessel. If desired, forpreparation of the salts according to the invention, it is also possibleto use a base polymer which has been prepared separately or which iscommercially available. Suitable polyurethanes are described, forexample, in DE-A-42 41 118, DE-A-42 25 045 and EP-A 0 619 111, to theentire contents of which reference is made. Suitable acrylate copolymersare described, for example, in DE-A-39 01 325 and DE-A-43 14 305, to theentire contents of which reference is made. Suitable solvents for thereaction are those mentioned above for the preparation of thepolyurethanes.

[0164] The neutralization of base polymers containing acid groups can becarried out by adding a base or a base mixture.

[0165] If, in the preparation of the polymeric salts, a water-miscibleorganic solvent is used, then this can be removed immediately afterwardby customary processes known to the person skilled in the art, eg. bydistillation at reduced pressure. Prior to removing the solvent, watercan be additionally added to the polymeric salt. Replacement of thesolvent by water gives a solution or dispersion of the polymeric salt,from which, if desired, the polymeric salt can be obtained in the usualmanner, e.g. by spray drying.

[0166] The pH of the aqueous solutions or dispersions of the polymericsalts can be adjusted by adding an acid or base. Suitable acids andbases are those mentioned above as additional neutralizing agents.Preferably, the pH for anionic polymeric salts is in the alkaline range,in particular >7.5. The pH for cationic polymeric salts is preferably inthe acidic range, in particular from 5.5 to 6.5.

[0167] The polymeric salts according to the invention are water-solubleor water-dispersible. They generally form clear and tack-free films andcan be washed out very easily with water. Advantageously, the polymericsalts according to the invention also give films with very goodelasticity. This is generally higher than the elasticity which isusually obtained for polyurethanes known from the prior art usingshort-chain neutralizing agents.

[0168] For the purposes of the present invention, the terms “alkyl”, and“alkylene” include straight-chain and branched alkyl or alkylene groups.These are preferably straight-chain or branched, C₁- to C₄₀- and,particularly preferably, C₂- to C₃₀-alkyl and alkylene groups.

[0169] C₁- to C₆-alkyl is preferably methyl, ethyl, isopropyl, n-butyl,2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl,3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,3-dinethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl,3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl etc.

[0170] C₂- to C₆-alkylene stands for straight and branched C₂- toC₆-alkylene radicals, preferably C₂- to C₄-alkylene radicals. Thesepreferably include ethylene, propylene, propane-1,3-diyl,butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, butane-2,3-diyl,2-methylpropane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl,pentane-1,3-diyl, pentane-1,2-diyl, 1-methylbutane-1,4-diyl,2-methylbutane-1,4-diyl, hexane-1,6-diyl, hexane-1,5-diyl,hexane-1,4-diyl, hexan-1,3-diyl, hexan-1,2-diyl etc.

[0171] C₆- to C₄₀-alkenyl preferably stands for straight and branchedalkylene groups which can be mono-, di- or polyunsaturated. It ispreferably C₉- to C₃₅-, in particular C₁₀- to C₃₀- and specifically C₁₂-to C₂₆-alkenyl groups. These include, in particular, hexenyl, heptenyl,octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,nonadecenyl, linolyl, linolenyl, elaostearylyl etc.

[0172] The anionogenic groups are carboxylic acid groups and/or sulfonicacid groups and/or phosphate and/or phosphonate groups.

[0173] The anionic groups are preferably carboxylate and/or sulfonategroups. As counterion, these preferably have an alkali metal, inparticular Na or K, or an ammonium ion derived from ammonia or aprimary, secondary or tertiary amine which is different to the aminesused as neutralizing agents.

[0174] The cationic groups are primary, secondary and, particularly,tertiary amines. Cationic groups are the protonation and/orquaternization product of an amine and, preferably, the product of thereaction with a mineral acid, such as hydrochloric acid or sulfuricacid, or the product of the reaction with a quaternizing agent. Thecustomary alkylating agents are suitable for the quaternization.

[0175] The quaternizing agents introduce a C₁-C₆-alkyl,C₅-C₈-cycloalkyl, phenyl, phenyl-C₁-C₄-alkyl.

[0176] Suitable N-vinylamides are N-vinylformamide, N-vinylacetamide,N-vinylpropionamide etc. Preference is given to using N-vinylformamide.

[0177] Suitable N-vinyllactams and derivatives thereof are those whichcan have, for example, one or more C₁-C₆-alkyl substituents, such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl etc.These include, for example, N-vinylpyrrolidone, N-vinylpiperidine,N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone,N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidine,N-vinyl-6-ethyl-2-piperidine, N-vinyl-7-methyl-2-caprolactam,N-vinyl-7-ethyl-2-caprolactam etc.

[0178] Suitable amine-containing monomers are, for example, those of thefollowing formula

[0179] where

[0180] R′=H, CH₃

[0181] X=O, NH

[0182] R′″, R″″=are identical or different and can represent CH₃, —C₂H₅,—C₃H₇, —C₄H₉, —tert-C₄H₉,

[0183] p=1 to 5

[0184] Particularly suitable monomers are:

[0185] N,N-Dimethylaminoethyl (meth)acrylate

[0186] N,N-Dimethylaminopropyl (meth)acrylate

[0187] N,N-Dimethylaminoethyl (meth)acrylamide

[0188] N,N-Dimethylaminopropyl (meth)acrylamide.

[0189] Very particularly suitable monomers are:

[0190] N,N-Dimethylaminoethyl methacrylate

[0191] N,N-Dimethylaminoethyl methacrylamide

[0192] N,N-Dimethylaminopropyl methacrylamide.

[0193] Suitable COOH-containing monomers are, for example,α-,β-ethylenically unsaturated mono- and dicarboxylic acids, such as,for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid,itaconic acid, crotonic acid and mixtures thereof. Preference is givento using acrylic acid, methacrylic acid and mixtures thereof.

[0194] The polymeric salts according to the invention and the polyureasaccording to the invention (summarized under the term polymers accordingto the invention) are particularly highly suitable as or in (a)hair-setting polymer(s) which impart flexibility to the hair.

[0195] The polymers according to the invention are suitable asauxiliaries in cosmetics. The invention therefore further relates to theuse of the polymers according to the invention in cosmetic compositions,in particular as film formers and/or coating compositions and/orbinders. In this connection, their use is possible, in particular incosmetic compositions for the treatment of keratin-containing andkeratin-analogous surfaces such as hair, skin and nails. They areparticularly suitable for hair cosmetics, preferably as setting polymersin hairsprays, setting foams, hair mousse, hair gel and shampoos. Theyare furthermore preferably suitable for use in pigment-containingcosmetic compositions, such as in decorative cosmetics, in particular inmascara and eyeshadows. They are also suitable for the preparation ofstick-shaped cosmetic products, such as deodorant sticks, make-upsticks, etc.

[0196] The polymers according to the invention are also suitable asauxiliaries in pharmacy, preferably as or in coating composition(s) orbinder(s) for solid medicament forms. The invention therefore furtherrelates to the use of the polymers according to the invention inpharmaceutical compositions, in particular as film formers and/orcoating compositions and/or binders. Thus, the abovementioned polymerscan be used as tablet coatings and tablet binders.

[0197] The polymers according to the invention are also preferablysuitable for use as or in coating composition(s) for the textile, paper,printing, leather and adhesives industry.

[0198] The polymers according to the invention are suitable asconstituent, as active polymer, film former, coating, binder,(co)emulsifier, penetration inhibitor, crystallization inhibitor,moisture-retention additives.

[0199] The polymers according to the invention are also suitable asviscosity-regulating agents. Particularly in the case of oil- andwater-containing cosmetic compositions, such as, for example, creams orlotions, it is possible, depending on the respective oil and watercontent, to adjust the viscosity to the desired value in a targetedmanner by adding the polymers according to the invention.

[0200] The invention further relates to a cosmetic and/or pharmaceuticalcomposition which comprises at least one polymer according to theinvention (=polyurea as claimed in claim 1 or polymeric salt). Thecomposition generally comprises the polymers according to the inventionin an amount in the range from about 0.2 to 30% by weight, in particularfrom 0.5 to 20% by weight, based on the total weight of the composition.

[0201] If the polymers according to the invention used in thecompositions according to the invention are water-dispersible, they canbe used in the form of aqueous dispersions having particle diameters ofcustomarily from 1 to 350 nm, preferably from 1 to 250 nm. The solidscontents of the preparations are usually in a range from about 0.2 to30, in particular from 0.5 to 20% by weight, preferably from 1 to 12% byweight. These microdispersions do not generally require emulsifiers orsurfactants for their stabilization.

[0202] The compositions according to the invention can preferably be inthe form of a hair-treatment composition, such as setting foam, hairmousse, hair gel, shampoo and, in particular, in the form of ahairspray. For use as conditioning polymer or setting polymer,preference is given to compositions which comprise the polymersaccording to the invention which have at least one glass transitiontemperature T_(g)≧10° C., preferably ≧20° C. The K value of thesepolymers (measured in accordance with E. Fikentscher, Cellulose-Chemie13 (1932), p. 58-64) using a 1% strength by weight solution inN-methylpyrrolidone is preferably in a range from 23 to 90, inparticular from 25 to 60.

[0203] If the polymeric salts according to the invention have siloxanegroups, then the siloxane content of these polymers is generally from0.05 to 20% by weight, based on the total weight of the incorporatedcomponents.

[0204] The cosmetic compositions according to the invention arepreferably hair-treatment compositions. These are usually in the form ofan aqueous dispersion or in the form of an alcoholic oraqueous-alcoholic solution. Examples of suitable alcohols are ethanol,propanol, isopropanol etc.

[0205] Furthermore, the hair-treatment compositions according to theinvention can generally comprise customary cosmetic auxiliaries, forexample plasticizers, such as glycerol and glycol; emollients; perfumes,surfactants, UV absorbers; dyes, antistatics; agents for improvingcombability; preservatives; and antifoams.

[0206] If the cosmetic compositions according to the invention areformulated as hairspray, they comprise a sufficient amount of apropellant, for example a low-boiling hydrocarbon or ether, such aspropane, butane, isobutane or dimethyl ether. Other propellants whichcan be used are compressed gases, such as nitrogen, air or carbondioxide. The amount of propellant can thus be kept low, in order not toincrease the VOC content unnecessarily. It is then generally no morethan 55% by weight, based on the total weight of the composition.However, higher VOC contents of 85% by weight and above are alsopossible, if desired.

[0207] The polymers according to the invention can also be used incombination with other polymers in the compositions. The polymersaccording to the invention are therefore also suitable for improving theelasticity of traditional hair-treatment compositions, in particularhair-setting compositions. These then impart very good flexibility andsuppleness to the hair.

[0208] Such other polymers are, in particular:

[0209] nonionic, water-soluble or water-dispersible polymers oroligomers, such as polyvinylcaprolactam, e.g. Luviskol Plus (BASF), orpolyvinylpyrrolidone and copolymers thereof, in particular with vinylesters, such as vinyl acetate, e.g. Luviskol VA 37 (BASF); polyamides,e.g. based on itaconic acid and aliphatic diamines;

[0210] amphoteric or zwitterionic polymers, such as theoctylacrylamide/methyl methacrylate/tert-butylaminoethylmetbacrylate/2-hydroxypropyl methacrylate copolymers obtainable underthe names Amphomer® (National Starch), and zwitterionic polymers, asdisclosed, for example, in German Patent Applications DE 39 29 973, DE21 50 557, DE 28 17 369 and DE 37 08 451.Acrylamidopropyltrimethylammonium chloride/acrylic acid or methacrylicacid copolymers and their alkali metal and ammonium salts are preferredzwitterionic polymers. Other suitable zwitterionic polymers aremethacrylethylbetain/methacrylate copolymers, which are availablecommercially under the name Amersette® (AMERCHOL), and copolymers ofhydroxyethyl methacrylate, methyl methacrylate, N,N-dimethylaminoethylmethacrylate and acrylic acid (Jordapon®);

[0211] anionic polymers, such as vinyl acetate/crotonic acid copolymers,as are sold, for example, under the names Resyn® (NATIONAL STARCH),Luviset® (BASF) and Gafset® (GAF) vinylpyrrolidone/vinyl acrylatecopolymers, obtainable for example under the trade name Luviflex®(BASF). A preferred polymer is the vinylpyrrolidone/acrylate terpolymerobtainable under the name Luviflex® VBM-35 (BASF). Acrylic acid/ethylacrylate/ N-tert-butylacrylamide terpolymers, which are sold, forexample, under the name Ultrahold® strong (BASF), and Luvimer® (BASF,terpolymer of t-butyl acrylate, ethyl acrylate and methacrylic acid),sodium sulfonate-containing amides or sodium sulfonate-containingpolyesters, or

[0212] cationic (quaternized) polymers, e.g. cationic polyacrylatecopolymers based on N-vinyllactams and their derivatives(N-vinylpyrrolidone, N-vinylcaprolactam etc.), and customary cationichair conditioning polymers, e.g. Luviquat® (copolymer ofvinylpyrrolidone and vinylimidazolium methochloride), Luviquat® Hold(copolymer of quaternized N-vinylimidazole, N-vinylpyrrolidone andN-vinylcaprolactam), Merquat® (polymer based on dimethyldiallylammoniumchloride), Gafquat® (quaternary polymers, which are formed by reactionof polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR(hydroxyethylcellulose with cationic groups), polyquaternium grades(CTFA names) etc.;

[0213] nonionic, siloxane-containing, water-soluble or - dispersiblepolymers, e.g. polyether siloxanes, such as Tegopren® (Goldschmidt) orBelsil® (Wacker).

[0214] The polymers according to the invention can be used in admixturewith an amide-containing polymer. Examples thereof include thepolyurethanes described in DE-A-42 25 045, the abovedescribedvinylpyrrolidone/acrylate terpolymers and acrylic acid/ethylacrylate/N-tert-butylacrylamide terpolymers (e.g. Ultrahold® strong fromBASF AG), the abovementioned amide-containing amphoteric polymers (e.g.Amphomer®) and in particular copolymers which have a proportion ofamide-containing monomers, such as N-vinyllactams, of at least 30% byweight (e.g. Luviskol®plus and Luviskol®VA37 from BASF AG).

[0215] The other polymers are preferably present in amounts up to 10% byweight, based on the total weight of the composition.

[0216] A preferred hair-treatment composition comprises:

[0217] from 0.2 to 30, in particular from 0.5 to 20% by weight,preferably from 1 to 10% by weight, of at least one polymer according tothe invention (polyurea as claimed in claim 1 and polymeric salts asclaimed in claim 5),

[0218] from 50 to 99.5% by weight, preferably from 55 to 99% by weight,of a solvent chosen from water and water-miscible solvents, preferablyC₂- to C₅-alcohols, in particular ethanol, and mixtures thereof,

[0219] from 0 to 70% by weight, preferably from 0.1 to 50% by weight, ofa propellant,

[0220] The propellant used is usually propane/butane, preferablydimethyl ether,

[0221] from 0 to 10% by weight, preferably from 0.1 to 10% by weight, ofat least one water-soluble or -dispersible polymer which is differentfrom the polymers according to the invention,

[0222] from 0 to 0.5% by weight, preferably from 0.001 to 2% by weight,of at least one water-soluble or water-dispersible silicone compound.

[0223] The composition according to the invention can comprise, assilicone compound, at least one nonionic, siloxane-containing,water-soluble or -dispersible polymer, in particular chosen from theabovementioned polyether siloxanes. The proportion of this component isthen generally from about 0.001 to 2% by weight, based on the totalweight of the composition.

[0224] The composition according to the invention can comprise, asadditional component, at least one water-insoluble silicone, inparticular a polydimethylsiloxane, e.g. the Abil® grades fromGoldschmidt. The proportion of this component is then generally fromabout 0.0001 to 0.2% by weight, preferably from 0.001 to 0.1% by weight,based on the total weight of the composition.

[0225] The composition according to the invention can optionallyadditionally comprise an antifoam, e.g. based on silicone. The amount ofthe antifoam is then generally up to about 0.001% by weight, based onthe total amount of the composition.

[0226] In addition to the abovementioned components, the compositionaccording to the invention preferably comprises:

[0227] from 0 to 40% by weight, preferably from 0.1 to 35% by weight, ofat least one surfactant,

[0228] from 0 to 5.0% by weight of an emulsifier,

[0229] from 0 to 3% by weight, preferably from 0.05 to 2.5% by weight,of at least one salt,

[0230] from 0 to 3% by weight, preferably from 0.05 to 2.5% by weight,of at least one thickener, and optionally other customary additives.Other additives which may be mentioned are: dyes, pigments, UV absorbers(each of which can be used in amounts from 0 to 5.0% by weight), andpreservatives and perfumes. These are then generally present in eachcase in an amount of from about 0 to 0.2% by weight, preferably from0.001 to 0.2% by weight.

[0231] All of the stated weight data relate to the total weight of thecomposition.

[0232] The compositions according to the invention have the advantagethat, on the one hand, they impart the desired hold to hair and thepolymers can be readily washed out (are redispersible), and, on theother hand, the hair remains elastic, supple and tack-free.

[0233] The invention is illustrated in more detail by reference to thefollowing, nonlimiting examples.

EXAMPLES

[0234] The assessment of the flexibility of the polymers was determinedas follows:

[0235] Strips of from 2 to 5 mm in width are stamped out of a 20%strength polymer solution having a layer thickness of from 90 to 140 μm,and tested for feel, strength and flexibility. In the test fortackiness, clarity and wash-off, a glass plate is coated with the filmsfor the testing.

[0236] For the valuation,

[0237] either a 20% strength ethanolic solution is coated onto PE filmand dried to give a 500 μm film.

[0238] elasticity: brittle (4)/hard (3)/moderate (2)/very soft (1)

[0239] tensile strength: flowing (4)/poor (3)/moderate(2)/solid (1)

[0240] feel: rough, impeding (4)/impeding(3)/good (2)/supple-smooth (1)

[0241] or a 5% strength aqueous ethanolic solution is coated on glassplates to give films

[0242] tackiness: tacky (4)/slightly tacky (3)/satisfactory(2)/non-tacky (1)

[0243] wash-off: insoluble (4)/poor (3)/satisfactory (2)/clear (1)

Examples 1 to 4 Preparation of Neutralizing Polymers

[0244] The neutralizing polymer is either polymerized from diolcomponents/diisocyanate in methyl ethyl ketone or acetone under pressureat 80° C. for about 5 h, or from diamine/diisocyanate at a temperatureof from 10 to 40° C. in ethanol.

[0245] Example: PEG1500 A-Si2122 PEG-DA MDPTA Hex-DA IPDI 1 3 — — 1 1.25 2 3 0.5 — 1 0.7 5 3 — 0.5 3 1 0.7 5 4 — — 3 1 1.2 5

Examples 5 - 9 Cationic Neutralizing Polymer Based on Polyurethane (PUR)for COOH-Containing Polymers

[0246] General Preparation Procedures:

[0247] For Example 7:

[0248] A four-necked flask, which had been fitted under an N₂ atmospherewith a stirrer, dropping funnel, thermometer and reflux condenser, wascharged with 88.9 g (0.4 mol) of isophorone diisocyanate in 20 g ofethanol. At a temperature of about 10° C., a mixture of 90 g (0.1 mol)of Tegomer A-Si 2122 (M_(n)=900 g/mol) and 30 g of ethanol was addeddropwise with stirring and ice cooling at a temperature of ≦40° C. Thereaction was maintained at about from 30 to 40° C. under stirring for afurther 30 minutes. After cooling to about 10° C., a mixture of 70 g(0.3 mol) of 0,0′-bis-(2-aminopropyl)polyether glycol 800; Mn≈900(Fluka) and 2.9 g (0.02 mol) of N-methyldipropylenetriamine in 50 g ofethanol was added, and the reaction temperature increased to about 45°C. The reaction mixture was then diluted with 600 g of ethanol.Filtration gave a clear pale yellow approximately 40% strength ethanolicpolymer solution.

[0249] The neutralization polymers of Examples 5, 6, 8, 9 and also 12and 13 were prepared in an analogous manner. SO₃NA- MAN NeutralizingPEG-DA MDPTA A-Si2122 PPG-DA 0078 IPDI Ex. polymer (mol) (mol) (mol)(mol) (mol) (mol) AV 5 A 3.5 1   — — — 4 ca. 20 6 B 4.0 —   0.5 — — 411.4 7 C 3.0 0.2 1 — — 4 7.5 8 D 3.0 — 1 0.2 — 4 4.8 9 E 3.5 2-3 — — 0.26 10

Example 10 Cationic Neutralizing Polymer Based on Polyacrylates (PA) forCOOH-Containing Polymers

[0250] General Preparation Procedures:

[0251] For Example 10: Feed 1: vinylpyrrolidone 59.5 g vinylcaprolactam102.0 g  dimethylaminopropylmethacrylamide  8.5 g Feed 2: ethanol 80.0 gt-butylperpivalate  0.4 g Feed 3: ethanol 80.0 g t-butylperpivalate  1.6g Initial charge: ethanol 95.0 g Feed 1 32.0 g Feed 2 10.0 g

[0252] Method:

[0253] Heat the initial charge to 80° C. under N₂ in a stirringapparatus fitted with 3 feed units and with stirring. Then start Feed 1and 2. Meter in Feed 1 in 3 h, and Feed 2 in 4 h. Afterpolymerize for 5h at 80° C. Start Feed 3 and add at 80° C. in 1 h, and afterpolymerizefor 5 h at 80° C. A colorless 40% strength ethanolic polyacrylatesolution was obtained.

[0254] The neutralizing polymer 11 was prepared in an analogous manner.DMA Ex. Neutralizing polymer VP VCap nBA PMA AV 10 F 35 60 — 5 16.5 11 G55 — 40 5 16.5

Example 12 and 13 Anionic Neutralizing Polymer Based on Polyurethane(PUR) for Amino-Containing Polymers

[0255] Neutralizing IPDI Ex. polymer PEG-DA A-Si2122 DMPA (mol) AV 12 H3.0 — 1 4 15 13 J 2.5 0.5 1 4 15

Examples 14 to 16 Catonic Neutralizing Polymers

[0256] Neutralizing Belsil Ex. polymer VP nBA TBA DMAPMA MAA 6031 AV 14K 70 — 21 6 3 — 19.8 15 L — 90 — 5 5 — 16.5 16 M — — 70 3 22  5 9.9

Example 17 Preparation of COOH-Containing PolyurethanePUR^({circle over (−)}) (Base Polymer I)

[0257] PUR of polyester-diol/neopentyl glycol/dimethylolpropanoicacid/isophorone diisocyanate

[0258] 500 g [0.5 mol] of polyester-diol of isophthalic acid/adipic acidand 1,6-hexanediol (Mw=1000 g/mol), 201 g [1.5 mol] ofdimethylolpropanoic acid (DMPA) and 104 g [1 mol] of neopentyl glycol(NPG) were dissolved in 370 g of methyl ethyl ketone with heating to atemperature of 80° C. and with stirring in a four-necked flask which wasfitted with a stirrer, dropping funnel, thermometer, reflux condenserand equipment for operating under nitrogen. As soon as everything haddissolved, the reaction mixture was cooled to about 50° C. 699.3 g [3.15mol] of isophorone diisocyanate were then added dropwise, and thereaction temperature increased. The reaction mixture was then stirredunder reflux until the NCO content of the mixture remained virtuallyconstant. The mixture was then cooled to RT. The reaction product wasshortstopped with 132.6 g [1.48 mol] of 2-amino-2-methyl-1-propanol(AMP)/water at a temperature of ≦40° C., and 90% neutralized. Thesolvent was then distilled off under reduced pressure at 40° C. to givean aqueous dispersion. Pulverulent polyurethanes can be obtained byspray drying.

Example 18 Preparation of COOH-Containing PolyurethanePUR^({circle over (−)}) (Base Polymer II)

[0259] (PUR of polyester-diol/neopentyl glycol/dimethylolpropanoicacid/isophoronone diisocyanate/hexamethylene diisocyanate)

[0260] 500 g [0.5 mol] of polyester-diol of isophthalic acid/adipic acidand 1,6-hexanediol (Mw=1000 g/mol), 201 g [1.5 mol] ofdimethylolpropanoic acid (DMPA) and 104 g [1 mol] of neopentyl glycol(NPG) were dissolved in 370 g of methyl ethyl ketone with heating to atemperature of 80° C. and with stirring in a four-necked flask which wasfitted with a stirrer, dropping funnel, thermometer, reflux condenserand equipment for operating under nitrogen. As soon as everything haddissolved, the reaction mixture was cooled to about 50° C. A mixture of444 g [2 mol] of isophorone diisocyanate and 193.4 g [1.15 mol] ofhexamethylene diisocyanate were then added dropwise, and the reactiontemperature increased. The reaction mixture was then stirred underreflux until the NCO content of the mixture remained virtually constant.The mixture was then cooled to RT.

[0261] The reaction product was shortstopped with 132.6 g [1.48 mol] of2-amino-2-methyl-1-propanol (AMP)/water at a temperature of ≦40° C., and90% neutralized.

[0262] The solvent was then distilled off under reduced pressure at 40°C. to give an aqueous dispersion. Pulverulent polyurethanes can beobtained by spray drying.

Example 19

[0263] Preparation of polyacrylate of n-BA/TBA/MAA (40/35/25) (Basepolymer III) Feed 1: n-butyl acrylate (nBA) 120.0 g t-butyl acrylate(TBA) 105.0 g methacrylic acid (MAA)  75.0 g Feed 2: ethanol 100.0 gt-butyl perpivalate  0.9 g Initial charge: Feed 1  32.0 g Feed 2  10.0 9Feed 3: ethanol 150.0 g t-butyl perpiv.  1.6 g Feed 4: ethanol 200.0 g

[0264] Procedure: heat initial charge to 80° C. with stirring under N₂in a stirring apparatus fitted with 4 feed units. Then start Feed 1 and2, meter in Feed 1 over 3 h, and meter in Feed 2 over 4 h.Afterpolymerize for 2 h at 80° C. Start Feed 3 and add at 80° C. over 1h, then afterpolymerize for 5 h at 80° C. Upon cooling, dilute with Feed4.

Example 20

[0265] Preparation of COOH-containing polyacrylatePA^({circle over (−)}) (from tert-butyl acrylate and methacrylic acid75:25)

[0266] This product can be prepared by the general preparation procedurein Example 10.

Example 21

[0267] Preparation of amine-containing polyacrylatePA^({circle over (−)}) (from tert-butyl acrylate, vinylpyrrolidone andDMAPMA (dimethylaminopropylmethacrylamide) (40:45:15))

[0268] This product can be prepared by the general preparation procedurein Example 10.

Example 22 Comparative Examples C1 to C5

[0269] Elas- ticity Tensile Tack- Wash- No. grade strength Peel inessoff Clarity C1 Base polymer 3 2 2 1-2 1-2 1 (I) PU neutralized with AMPC2 Base polymer 2 2-3 2-3 2-3 1 1 (II) PU neutralized with AMP C3 Basepolymer 2-3 2-3 2 2-3 1 1 (III) PU neutralized with AMP C4 Neutralized 23 1-2 3-4 2 1 polymer (C) C5 Neutralized 2-3 2-3 2 3 1-2 1-2 polymer (G)

[0270] Examples according to the invention Base polymer: neutralizingElas- polymer ticity Tensile Tack- Wash- No.*) [weight ratio] gradestrength Feel iness off Clarity  1 (I):(A) = [9:1] 2 1-2 2 1 1-2 1-2  2(I):(B) = [9:1] 1-2 2 1 1 1-2 1  3 (I):(C) = [9:1] 1-2 2 1 1 1-2 1  4(I):(C) = [8:2] 1 2 1 1-2 1 1  5 (I):(C) = [7:3] 1 2-3 1 2 1 1  6(I):(D) = [9:1] 2 2 1-2 1 1 1  7 (I):(E) = [9:1] 1-2 1-2 1 1 1-2 1  8(II):(A) = [9:1] 1-2 2 2 2 1 1-2  9 (II):(B) = [9:1] 1 2-3 1-2 1-2 1 110 (II):(C) = [9:1] 1 2 1-2 1-2 1 1 11 (II):(D) = [9:1] 1-2 2 1-2 1-2 11 12 (II):(E) = [9:1] 1 2 1 1-2 1 1 13 (III):(A) = 2 2 2 2 1 1-2 [9:1]14 (III):(B) = 2 2-3 1-2 1-2 1 1 [9:1] 15 (III):(C) = 2 2-3 1-2 1-2 1 1[9:1] 16 (III):(D) = 2 2-3 1-2 1-2 1 1-2 [9:1] 17 (III):(E) = 2 2 1-21-2 1 1 [9:1] 18 (I):(F) = [7:3] 2-3 2 1-2 2 1 1 19 (I):(G) = [7:3] 2-32 2 1-2 1 1 20 (II):(F) = [8:2] 2 2-3 2 2 1 1 21 (II):(G) = [8:2] 2 2-32 1-2 1 1 22 (II):(G) = [6:4] 1-2 2-3 2 1-2 1 1 22a (I):(K) = [5:5] 3 21-2 1-2 1 1 22b (II):(K) = [5:5] 2 2 1-2 1-2 1 22c (II):(K) = [4:6] 2 21-2 1-2 1 1 22d (II):(L) = [5:5] 1-2 2 1-2 1-2 2-3 2 22e (II):(M) =[7:3] 1-2 2 1-2 1-2 1-2 1

Examples 23 to 25

[0271] Preparation of polymeric salts Neutralized with Lactic Curl acidWeight Weight Flexi- reten- Wash- (DN %) ratio*) ratio**) bility Holdtion off C PA^(⊕) 100 — — 3-4 1 78 1 23 PA^(⊕) 90 9:1 2-3 1 75 1 24PA^(⊕) 90 9:1 2-3 1 77 1 25 PA^(⊕) 90 8:2 2 1-2 74 1

Example 26

[0272] Use as hair-setting polymer [%] Aerosol hairspray Polymer No.1-22 3.00 Dimethyl ether 40.00 Ethanol 57.00 Other additives: silicone,perfume, antifoam . . . Aerosol hairspray Polymer No. 13-22 3.00Propane/butane gas 40.00 Ethanol 57.00 Other additives: silicone,perfume, antifoam . . . VOC 80 Aerosol hairspray Polymer No. 1-22 5.00Water 15.00 Dimethyl ether 40.00 Ethanol 40.00 Other additives:silicone, perfume, antifoam . . . VOC 55 Aerosol hairspray Polymer No.1-12 and 18-22 and 22a-e 3.00 Water 42.00 Dimethyl ether 35.00 Ethanol20.00 Other additives: silicone, perfume, antifoam . . . VOC 55 Handpump spray Polymer No. 1-12 and 18-22 and 22a-e 5.00 Water 20.00 Ethanol55.00 Other additives: silicone, perfume, antifoam . . . Setting foam(=mousse) Polymer No. 8-22 and 22a-e (25% strength 20.00 aqueoussolution) Cremophor A 25 (Ceteareth 25/BASF) 0.20 Comperlan KD (CocamideDEA/Henkel) 0.10 Water 69.70 Propane/butane 10.00 Other additives:perfume, preservatives . . .

[0273] Preparation: Weigh in and dissolve with stirring. Bottle and addpropellant. Conditioning shampoo [%] A) Texapon NSO 28% strength (SodiumLaureth 50.00 Sulphate/Henkel) Comperlan KD (Cocamide DEA/Henkel) 1.00Polymer 22, 22a-e (25% strength aqueous 20.00 solution) q.s. Perfume oilB) Water 27.50 Sodium chloride 1.50 q.s. preservatives . . .

[0274] Preparation: Weigh in and dissolve separately phases A and B withstirring and mix. Slowly stir phase B into phase A.

[0275] Standard O/W cream [%] Oil phase Paraffin oil 7.50 Ceteareth-6and stearyl alcohol 3.50 Ceteareth-25 3.50 Cetyl alcohol 3.50 Glycerylmonostearate s.e. 2.50 Cetearyl octanoate 3.20 Methyl- andpropyl-4-hydroxybenzoate (7:3) Tocopheryl acetate 1.00 Water phasePolymer 1-22 and 22a-e 1.50 Water 74.60 Imidazolidinylurea 0.10

[0276] Preparation: Weigh in and homogenize with stirring the oil phaseand water phase separately at a temperature of about 80° C. Slowly stirthe water phase into the oil phase. Slowly cool to RT with stirring.

We claim:
 1. A polyurea constructed from: a) a diamine which contains agroup —(—CH₂CH₂O—)_(n)-(C₃H₆-O—)_(m), where the order of the alkyleneoxide units is arbitrary and m and n independently of one another are aninteger between 0 and 50, and m+n is between 5 and 60, and b) at leastone amino-containing or hydroxyl-containing polysiloxane and c) at leastone duisocyanate, and d) optionally a di-, tri- or tetramine orpolyamnie which contains at least one ionogenic group, and e) optionallyone or more diamines having a molecular weight of from 60 to 6000 g/mol,where the polyurea contains at least one ionogenic or ionic group.
 2. Aprocess for the preparation of polyurea as claimed in claim 1, where thepolymerization is carried out in alcohol or water/alcohol solution at atemperature less than or equal to 50° C., and in the case ofhydroxyl-containing polysiloxanes the components b) and c) are firstlyreacted with one another.
 3. The use of neutralized polyurea as claimedin claim 1 as film-forming auxiliary or as additive for cosmeticpreparations.
 4. The use of polyurea as claimed in claim 1 having ionicor ionogenic groups as neutralizing polymer for polymers which containionic or ionogenic groups.
 5. A water-soluble or water-dispersiblepolymeric salt comprising A) a base polymer which contains an ionic orionogenic group, and B) a neutralizing polymer which partiallyneutralizes the ionic or ionogenic group of the base polymer A, wherethe ionogenic groups of the base polymer A are more frequent by a factorof from 2 to 30 than the ionogenic groups of the neutralizing polymer B.6. A water-soluble or water-dispersible polymeric salt as claimed inclaim 5, wherein the base polymer A and/or the neutralizing polymer Bare a polyurea or polyurethane.
 7. A water-soluble or water-dispersiblepolymeric salt as claimed in at least one of claims 5 and/or 6, whereinthe base polymer A and/or the neutralizing polymer B is a polyurea asclaimed in claim
 1. 8. A polyurethane, poly(urethane-urea) or polyureaas base polymer as claimed in at least one of claims 5 to 7, constructedfrom: f) at least one compound which contains two (or more) activehydrogen atoms per molecule, g) at least one compound which contains twoactive hydrogen atoms per molecule and has a molecular weight of from 56to 300 g/mol, h) at least one phosphate-, phosphonate-, COO⁻, SO₃ ⁻,and/or tert-amine-containing compound or compounds thereof which containthe free acids that contain two active hydrogen atoms per molecule, andi) at least one diisocyanate.
 9. A polyacrylate as base polymer A asclaimed in at least one of claims 5 to 7, constructed from: at least oneC₁-C₄-alkylacrylic ester or C₁-C₄-alkylmethacrylic ester or acrylamideor methacrylamide or C₁-C₄-alkylacrylamide or C₁-C₄-alkylmethacrylamide,at least one COOH-containing monomer.
 10. A neutralizing polymer B asclaimed in at least one of claims 5 to 7, which is a film-formingpolymer which is dispersible with water.
 11. A polyurea as claimed inclaim 1 as neutralizing polymer B as claimed in at least one of claims 5to
 7. 12. A polyurethane, poly(urethane-urea) or polyurea asneutralizing polymer B as in at least one of claims 5 to 7, constructedfrom: j) at least one compound or a mixture of compounds carrying atleast two active hydrogen atoms per molecule and having a molecularweight of from 56 to 6000 g/mol, where at least one compound containsone of the following groups: —(—CH₂-CH₂O—)_(m)-(C₃H₆O—)n—, where theorder of the alkylene oxide units is arbitrary, and m and nindependently of one another are an integer from 0 to 50, and the summ+n is in the range from 5 to 60, —COO⁻, —SO₃ ⁻ or —N⁺group-(quaternized amines), k) if necessary a compound having at leasttwo active hydrogen atoms per molecule and at least one ionogenic group,l) at least one amino-containing poly(dimethylsiloxane) and m) at leastone diisocyanate, where the acid value or amine value is not greaterthan
 60. 13. A neutralizing polymer as claimed in claim 12, where thecomponents are present in the following amounts: j) 10 to 90% by weightk) 0 to 20% by weight l) 0.1 to 30% by weight m) 5 to 30% by weight,based on j+k+l+m.
 14. A neutralizing polymer B as claimed in at leastone of claims 5 to 7, constructed from at least one vinyllactam and/orat least one vinylamide and at least one amine-containing monomer, wherethe amine value is between 1 and
 60. 15. A neutralizing polymer B asclaimed in at least one of claims 5 to 7, constructed from at least oneC₁-C₁₈-alkylmethacrylic ester and/or C₁-C₁₈-alkylmethacrylamide and atleast one amine-containing and/or COOH-containing monomer.
 16. A processfor the preparation of polymeric salts as in any of claims 5 to 15,where the base polymer A is partially neutralized in a suitable solventwith a monovalent neutralizing agent, and then the neutralizing polymerB is added.
 17. The use of a polymer as claimed in any of the precedingclaims, wherein the neutralized product has a glass transitiontemperature of >10° C., as setting polymer or as conditioning polymer inhair cosmetics, in particular for hair sprays, hair foams and shampoos.18. A cosmetic and/or pharmaceutical composition comprising at least onepolymer as claimed in any of the preceding claims.
 19. A hair-treatmentcomposition comprising 0.5-20% by weight of a polymer as claimed in anyof the preceding claims, 50-99.5% by weight of a solvent, 0-70% byweight of a propellant, 0-10% by weight of a commercially available hairpolymer, 0-0.5% by weight of a water-soluble or dispersible siliconecompound, 0-40% by weight of a surfactant, 0-5.0% by weight of anemulsifier, 0-3.0% by weight of a salt, 0-3.0% by weight of a thickener.20. The use of a polymer as claimed in any of the preceding claims incosmetic and/or pharmaceutical compositions.
 21. The use of a polymer asclaimed in any of the preceding claims in the textile, printing, paper,leather, adhesives and agrochemical industry.
 22. The use as claimed inclaim 21 and/or 22 as constituent, as active polymer, film former,coating, binder, (co)emulsifier, penetration inhibitor, crystallizationinhibitor and/or moisture-retention additives.
 23. The use as claimed inclaim 21 and/or 22 as viscosity regulator.